Airborne measurements of peroxy radicals using the PERCA technique

Abstract

The Peroxy Radical Chemical Amplifier (PERCA) technique is a proven method for measurement of ambient levels of peroxy radicals at ground level, but there are no published instances of the technique being used on an aerial platform. Here we describe deployment of a PERCA on the former UK Meteorological Office C-130 Hercules research aircraft. The instrument uses the established method of chemical amplification and conversion of peroxy radicals to nitrogen dioxide (NO₂) by doping the sample air-flow matrix with CO and NO, subsequently measuring the NO₂ yield with an improved ‘Luminox’ LMA-3 NO₂ detector. NO₂ from the amplification chemistry is distinguished from other sources of NO₂ reaching the detector by periodically injecting CO ∼1 s downstream of the NO injection point (termination mode). Chain lengths (CL's) for the amplification chemistry were typically ∼260 (ground level) to ∼200 (7,000 m). This variation with altitude is less than the variation associated with the ‘age’ of the PFA inlet material where the amplification chemistry occurs; CL's of ∼200 with old tubing to ∼300 with new clean tubing were typical (ground level values). The CL determinations were made in-flight using an onboard calibration unit based on the 254 nm photolysis of 7.5 to 10 parts per billion (by volume, ppbv) of CH₃I in air, producing CH₃O₂ in a quantitative manner. The noise-equivalent detection limit for peroxy radicals (HO₂ + RO₂) is 2 parts per trillion (by volume, pptv) at 3,650 m when the background ambient ozone levels are stable, based on a 5 min average of five 30 s amplification cycles and five 30 s termination cycles. This detection limit is a function of several factors but is most seriously degraded when there is large variability in the ambient ozone concentration. This paper describes the instrument design, considers its performance and proposes design improvements. It concludes that the performance of an airborne PERCA in the free troposphere can be superior to that of ground-based instruments when similar sampling frequencies are compared.